US4309213A - Process of encapsulation by interfacial polycondensation - Google Patents
Process of encapsulation by interfacial polycondensation Download PDFInfo
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- US4309213A US4309213A US05/973,164 US97316478A US4309213A US 4309213 A US4309213 A US 4309213A US 97316478 A US97316478 A US 97316478A US 4309213 A US4309213 A US 4309213A
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- Prior art keywords
- process according
- hydrophobic
- reagent
- amine
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
- B01J13/16—Interfacial polymerisation
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
- A01N25/28—Microcapsules or nanocapsules
Definitions
- the present invention relates to a process for the encapsulation of liquid substances by interfacial polycondensation. It also relates to the capsules obtained by this process.
- the encapsulation of liquid substances by interfacial polycondensation was discovered long ago.
- the principle of the method consists in bringing into contact a phase containing the liquid substance to be encapsulated and a polycondensation reagent, with another phase which is immiscible with the first and contains a second reagent capable of reacting with the first to give a polycondensation product.
- the two phases When the two phases are brought into contact, the two compounds react at the interface of the phases and, by polycondensation, create a wall of polymer around the drops of liquid substances.
- the capsules obtained can then be washed and dried before use.
- the disperse phase is organic, whilst the second phase, used as the dispersion medium, is aqueous. In other words, the reaction takes place in a dispersion of the "oil-in-water" type.
- the polymer constituting the wall of the capsules obtained can be a poly(sulphon)amide, a polyester, a polyether, a polyurethane or a polyurea or copolymers containing at least two types of unit chosen from ester, ether, (sulphon)amide, urethane and urea.
- the reagents which can be used in the formation of the above polymers or copolymers must be at least difunctional. The presence of more than two functional groups causes the polymer chains to crosslink with one another.
- one consists in carrying out the dispersion and the reaction simultaneously.
- an organic phase is prepared which contains the substance to be encapsulated, optionally with a solvent, and the hydrophobic reagent, and this phase is then dispersed in the aqueous phase containing the hydrophilic reagent.
- the reaction therefore takes place at the actual moment of dispersion.
- the fact that the two phenomena occur simultaneously exhibits the disadvantage that it leads to capsules having an excessively wide distribution of diameters.
- another technique consists in carrying out the process in two stages so as to separate the dispersion operation from the actual reaction.
- the organic phase as described above, is initially dispersed in water, and the hydrophilic reagent is then added to the dispersion.
- a process for encapsulation by interfacial polycondensation with a polyurea which consists, in a first stage, in dispersing in water an organic phase containing the substance to be encapsulated, and at least one polyisocyanate, and then, in a second stage, in starting the reaction by hydrolysing some of the functional groups of the polyisocyanate or polyisocyanates into amine functions, the latter then reacting immediately with the remaining polyisocyanates to give the polyurea.
- This technique is particularly suitable for this last field, because it provides compositions which liberate the active ingredients (insecticides, herbicides, fungicides and the like) in a controlled manner (passage across the polymer wall), thus permitting, in particular, a reduction in the amounts and a lowering of the toxicity on handling and on the crops. Furthermore, compared with other compositions which combine active ingredients and polymers, the compositions obtained by this technique exhibit the advantage that they use a much smaller amount of polymer, and this leads to a smaller amount of waste products in the environment of the treated crops.
- the subject of the present invention is therefore to provide a process which does not exhibit the disadvantages of these techniques.
- It relates to the process for the encapsulation of a liquid hydrophobic substance by interfacial polycondensation, which consists, in a first stage, in dispersing, in an aqueous phase, an organic phase containing the liquid hydrophobic substance to be encapsulated and at least one polyfunctional hydrophobic reagent having functional groups containing the carbonyl or sulphonyl group, and then, in a second stage, in causing the polycondensation of the hydrophobic reagent with at least one polyfunctional amine as a hydrophilic reagent, characterised in that, in the first stage, the aqueous phase contains the polyfunctional amine, the amine functions of which have been rendered unreactive by salification, and in that, in the second stage, the polycondensation is started by liberating the amine functions through the addition, to the aqueous phase, of an equivalent amount of a base which is stronger than the amine.
- the term "substance” is to be understood as meaning a liquid or solid compound which is essentially hydrophobic, that is to say virtually insoluble in water, and which is inert towards the hydrophobic reagents. If this substance is itself a liquid, it can be used in the process either directly or in the form of a solution or dispersion. If it is a solid, it must be either dissolved or suspended in an organic solvent beforehand. Therefore, in order to carry out the invention, the substance will always be in the form of a liquid and it is in this sense that the term "liquid substance” is applied in the description to this presentation of the substance.
- Any substance satisfying the above conditions is suitable for carrying out the invention, regardless of its final application, for example as a dyestuff, ink, pharmaceutical product, foodstuff, paint, cosmetic product, adhesive, catalyst, cleaning product, fireproofing agent, antioxidant and, in particular, as an active ingredient for plant health, such as a herbicide, insecticide, fungicide or growth regulator.
- a herbicide insecticide, fungicide or growth regulator.
- insecticides such as parathion-methyl and Chlormephos and with the herbicide Isoproturon.
- solvent which can be used for bringing the substance into a liquid form (solution or dispersion)
- aliphatic or aromatic, hydrophobic organic solvents for example cyclohexane, tetrachloroethylene, xylene, carbon tetrachloride, chloroform and 1,2-dichloroethane.
- hydrophobic reagents which can be used according to the invention are at least difunctional in order to enable the polycondensation reaction to take place. Furthermore, the functional groups must contain the carbonyl group ##STR1## or sulphonyl group ##STR2##
- the functional groups are respectively ##STR3## groups which are respectively characteristic of the carboxylic and sulphonic acid chlorides, and/or --N ⁇ C ⁇ O groups which are characteristic of the isocyanates.
- a poly(sulphon)amide will therefore be obtained; in the second case, a polyurea will be obtained.
- the process according to the invention can simultaneously employ two different types of hydrophobic reactant, for example a polyfunctional acid chloride with a polyfunctional isocyanate.
- a mixed polycondensation product referred to as a poly(sulphon)amide-urea, is then obtained.
- the hydrophilic reagents are primary or secondary amines which are at least difunctional and preferably di- or tri-functional.
- the crosslinking index of the polycondensation products is higher, the larger the number of functional groups carried by the hydrophobic and hydrophilic reagents.
- the term crosslinking index is to be understood as meaning half the sum of the mean number of functional groups per molecule of the hydrophilic reagents and of the hydrophobic reagents.
- the crosslinking of the polymeric material of the wall of the capsule is influenced particularly by varying the number of functional groups in the acid chlorides and, preferably, in the isocyanates and amines, this crosslinking largely determining the rate of liberation of the encapsulated substance.
- the polyfunctional acid chlorides which can be used according to the invention mainly include chlorides of saturated or unsaturated, aliphatic carboxylic acids, or of aromatic carboxylic acids, which can contain from 2 to 36 carbon atoms.
- the preferred aliphatic acids are linear acids.
- diacids which may be mentioned are, for the aliphatic diacids, oxalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, undecanedioic acid and dimeric acid (namely the dimer of linoleic acid), and, for the aromatic diacids, terephthalic acid.
- triacids which may be mentioned are trimesic acid and citric acid.
- chlorides of sulphonic acids such as benzene-1,3-disulphonic acid and benzene-1,3,5-trisulphonic acid.
- the organic polyfunctional isocyanates which can be used as hydrophobic reagents in the present process include aromatic isocyanates, in particular aromatic diisocyanates and triisocyanates, aliphatic diisocyanates, in particular high molecular weight, linear aliphatic diisocyanates, and prepolymers having a terminal isocyanate group, which are obtained by reacting a polyester, a polyether, a polyesterether having terminal hydroxyl groups, with a molecular weight of between 500 and 4,000, or mixtures of these polymers, with polyfunctional isocyanates.
- Examples which may be mentioned are 1-chloro-2,4-diisocyanatobenzene, 4,4'-diisocyanatodiphenylmethane, 1,6-diisocyanatohexane, diisocyanatonaphthalenes and, preferably, 2,4- or 2,6-diisocyanatotoluene or mixtures containing respectively 60/80% of the 2,4 isomer and 40/20% of the 2,6 isomer, and also polymethylene-polyphenylisocyanate.
- organic polyisocyanates can either be used by themselves or in mixtures.
- mixtures based on polymethylene-polyphenylisocyanate and on diisocyanatotoluene (containing 80% of the 2,4 isomer and 20% of the 2,6 isomer) make it possible to obtain capsule walls possessing good properties of controlled liberation of the substance.
- the amount of hydrophobic reagent(s) which is to be employed in the process according to the invention determines the proportion of wall in the capsule. In practice, proportions of 5 to 50% by weight of the organic phase will be preferred. In fact, below 5%, the wall of the capsules obtained no longer has adequate mechanical characteristics; above 50%, the proportion of polymer becomes economically less valuable and, in many cases, of no technical value.
- difunctional aliphatic or aromatic amines such as, for example, preferably, ethylenediamine but also phenylenediamines, toluenediamines, hexamethylenediamine or piperazine, and also amines having more than two functional groups, such as, preferably, diethylenetriamine but also bis-(hexamethylene)-triamine, 1,3,5-tri
- each of the two immiscible phases is initially prepared.
- the organic phase is obtained by mixing the liquid substance to be encapsulated, with the hydrophobic reagent or reagents in the proportions indicated above. This mixing takes place with dissolution, if the liquid substance is homogeneous (with or without solvent), or with dispersion, if the liquid substance is itself a dispersion or suspension in an organic solvent.
- the aqueous phase is prepared by dissolution of a water-soluble salt which is obtained beforehand by salifying the polyfunctional amine with a strong inorganic acid, such as a hydrogen halide acid, in particular hydrochloric acid, or a perhalic acid, or a strong organic acid, in particular acetic acid, methanesulphonic acid, benzenesulphonic acid or para-toluenesulphonic acid.
- a strong inorganic acid such as a hydrogen halide acid, in particular hydrochloric acid, or a perhalic acid, or a strong organic acid, in particular acetic acid, methanesulphonic acid, benzenesulphonic acid or para-toluenesulphonic acid.
- the solution thus obtained is generally acid, the acidity of the amine salt being a function of that of the salifying acid and of the basicity of the amine.
- Anionic, cationic or non-ionic surface-active agents which are customary in interfacial polycon
- a protective colloid to the aqueous phase is frequently advisable and this can be carried out either before or after dispersion.
- suitable protective colloids which may be mentioned are polyacrylates, methylcellulose, polyvinyl alcohol which is optionally more or less esterified or etherified, and polyacrylamide.
- the adjuvants are usually added at the rate of 0.1 to 5% by weight of the aqueous phase. In some cases, the properties of these colloids can make it necessary to additionally employ anti-foam agents, in particular those based on silicones.
- the aqueous phase can advantageously be homogenised by stirring.
- the first stage which is characteristic of the process according to the invention, that is to say dispersion, for example by running the organic phase into the aqueous phase, preferably whilst stirring vigorously, for example using a turbine stirrer, in order to thoroughly distribute, in the medium, the droplets which form, and in order to determine and regularise their size.
- the stirring force is advantageously regulated so that the droplets have a dimension ranging from about 1 micron to 100 microns. Larger dimensions are possible, but most frequently provide no additional advantage.
- the polycondensation reaction is started by liberating the polyfunctional amine or amines through the addition, to the dispersion medium, of a base which is at least as strong as the amine functions of the hydrophilic reagent.
- This base can either be a hydroxide, preferably an alkali metal hydroxide, or a salt of a weak acid and a strong base. In practice, sodium hydroxide, potassium hydroxide or ammonia is used. Of course, this base must be added to the dispersion in an approximately stoichiometric amount.
- the stirring of the dispersion is continued, but in a more moderate manner, for a period of about 1 to 5 hours at a temperature which is normally between about 0° C. and ambient temperature.
- a temperature which is normally between about 0° C. and ambient temperature.
- the process described above has been presented as a discontinuous operation, but it can be adapted for continuous operation, in particular by regulating the rate of introduction of the reagents, the rate at which the capsules are drawn off and the speed at which the dispersion is stirred.
- the capsules obtained in accordance with the process are optionally separated from the aqueous phase, in a manner which is in itself known, and then washed until the pH of the washings is approximately neutral and dried. They are then ready for use, either as obtained or in an aqueous dispersion or emulsion, depending on the nature and the properties of the encapsulated substance, and also on the desired application.
- Solution A is introduced into a one liter cylindrical reactor equipped with a turbine stirrer having a high rate of shear, and with a frame stirrer for carrying out more moderate stirring.
- the organic solution B is rapidly run into this solution, stirred by the turbine stirrer. After about 45 seconds, the dispersion is satisfactory, the turbine is stopped and the experiment is continued using the frame stirrer. As soon as the turbines are stopped, the aqueous sodium hydroxide solution C is rapidly run in.
- the microcapsules are filtered off and washed until the pH of the washings is neutral.
- Capsules C 1 containing parathion-methyl, are obtained, the sizes of which range from 20 to 40 microns and in which the crosslinking index of the polyurea constituting the wall is 2.53.
- Example 1 The procedure of Example 1 is followed, using the following mixtures A, B and C:
- Capsules C 2 are obtained, the dimensions of which are similar to those above and the wall of which is a linear polyamide (crosslinking index 2.00).
- Example 1 The procedure of Example 1 is followed, using the following mixtures A, B and C:
- Capsules C 3 are obtained, the dimensions of which are similar to those above and the wall of which is a polyamide-urea having a crosslinking index of 2.07.
- Example 1 The procedure of Example 1 is followed, using the following mixtures A, B and C:
- Capsules C 4 are obtained, the dimensions of which are similar to those above and the wall of which is a polyamide-urea having a crosslinking index of 2.27.
- the capsules are used in the form of an aqueous suspension containing 200 g/liter of active ingredient.
- a spray pass bean plants at the stage of two fully open cotyledon leaves are treated, after having destroyed the apical bud, with an aqueous suspension or emulsion of the active ingredient to be tested, until dripping wet, in accordance with a scale of doses expressed in g/hl.
- Discs of leaf are taken from the treated plants after a variable time, either immediately (DO) or after an increasing number of days (D+1, D+4, D+8, D+15, D+21 or D+30), and each disc is placed in a Petri dish, into which are introduced 5 cotton-moth (Spodoptera littoralis) caterpillars, at the 3rd larval stage, in order to check the effectiveness of the residual material as an insecticide.
- Each Petri dish is then kept in the dark in an enclosure at a temperature of 25° C. and a relative humidity of 70%. 48 hours after contact, the dead and live caterpillars are counted.
- the following table gives the mortality rates for each formulation tested, at a dose of 50 g/hl of active ingredient, as a function of time.
- the tests of acute oral toxicity in rats have shown that the encapsulated formulation has an LD 50 of about 38 mg of active ingredient/kg, that is to say about seven times that of the commercial formulation, also expressed in equivalents of pure parathion-methyl.
- the formulation according to the invention is seven times less toxic than the reference, and this is remarkable.
- Example 1 The procedure of Example 1 is followed, using the following mixtures A, B and C:
- microcapsules After filtration and washing, microcapsules are obtained, the wall of which is a polyurea having a cross-linking index of 2.53. The rate of liberation of the insecticide is substantially reduced.
- Example 1 The procedure of Example 1 is followed, using the following mixtures A, B and C:
- the capsules (C 7 ) are formulated into an aqueous suspension containing 30% (weight/weight) of active ingredient.
- Example 1 The procedure of Example 1 is followed, using the following mixtures A, B and C:
- the capsules (C 8 ) are formulated into an aqueous suspension containing 30% (weight/weight) of active ingredient.
- Example 8 The residual biological activity of Chlormephos microencapsulated in accordance with the process illustrated in Example 8 is studied in comparison with a commercial formulation in the form of a granulate containing 5% by weight of active ingredient.
- Loam is mixed, respectively, by grinding with an aqueous suspension of the capsules obtained in Example 8 and by stirring in the case of the granules.
- the mixing is carried out so that the dosage of active ingredient is the same in the two cases and equal to 2 kg/ha.
- the mixture is introduced into pots. On the surface of the treated earth there are placed, per pot, 50 four-day old larvae of flies (Musca domestica). Each test is carried out twice.
- Chlormephos encapsulated by the process of the invention possesses not only an immediate insecticidal activity, which is as good as Chlormephos granulate but which is also more persistent, even though the granules are known to ensure a progressive release of the active ingredient.
- Pieces of filter paper placed at the bottom of Petri dishes are treated, by spraying, with 0.5 ml of a dispersion of an emulsifiable concentrate of Chlormephos capsules obtained in Example 8.
- commercial Chlormephos granules (containing 5% by weight of active ingredient) are stuck by moistening onto filter papers placed at the bottom of Petri dishes.
- the surface of the filter papers and the quantity, in concentration of active ingredient applied, is calculated to correspond to a dosage of 10 kg/ha in treatment in the open field ("localized strip" treatment).
- Seed wheat is placed on the filter paper.
- Example 1 The procedure of Example 1 is followed, using the following suspension B and solutions A and C:
- microcapsules After filtration and washing, 379 g of an aqueous suspension of microcapsules are recovered, which contain 24.5% by weight of N-(p-isopropylphenyl)-N,N'-dimethylurea (Isoproturon).
- the wall of the microcapsules is a polyurea and the diameters are between 2 and 140 microns. The rate of liberation of the herbicide in water is substantially reduced.
- Example 1 The procedure of Example 1 is followed, using the following mixtures A, B and C:
- the product After filtration and washing until the pH of the washings is neutral, the product is dried at 60° C. in a stream of air.
- Example 1 The procedure of Example 1 is followed, using the following mixtures A, B and C:
- the product After filtration and washing until the pH of the washings is neutral, the product is dried at 60° C. in a stream of air. This gives a powder which is dry to the touch and consists of 2 to 25 ⁇ microcapsules containing about 50% of triphenylphosphine, 27% of xylene and 23% of polyurea constituting the walls.
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Zoology (AREA)
- Pest Control & Pesticides (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Environmental Sciences (AREA)
- Toxicology (AREA)
- Dispersion Chemistry (AREA)
- Agronomy & Crop Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
- Fireproofing Substances (AREA)
- Polyamides (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR7739950 | 1977-12-30 | ||
FR7739950A FR2413123A1 (fr) | 1977-12-30 | 1977-12-30 | Procede d'encapsulation par polycondensation interfaciale |
Publications (1)
Publication Number | Publication Date |
---|---|
US4309213A true US4309213A (en) | 1982-01-05 |
Family
ID=9199623
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US05/973,164 Expired - Lifetime US4309213A (en) | 1977-12-30 | 1978-12-26 | Process of encapsulation by interfacial polycondensation |
Country Status (30)
Country | Link |
---|---|
US (1) | US4309213A (fr) |
JP (1) | JPS54135671A (fr) |
AR (1) | AR221228A1 (fr) |
AT (1) | AT365097B (fr) |
AU (1) | AU522021B2 (fr) |
BE (1) | BE873248A (fr) |
BR (1) | BR7808615A (fr) |
CA (1) | CA1129725A (fr) |
CH (1) | CH643155A5 (fr) |
CS (1) | CS208771B2 (fr) |
DD (1) | DD141113A5 (fr) |
DE (1) | DE2855065A1 (fr) |
DK (1) | DK149341C (fr) |
ES (1) | ES476279A1 (fr) |
FR (1) | FR2413123A1 (fr) |
GB (1) | GB2011341B (fr) |
HU (1) | HU180275B (fr) |
IE (1) | IE47702B1 (fr) |
IL (1) | IL56331A (fr) |
IN (1) | IN150286B (fr) |
IT (1) | IT1102793B (fr) |
LU (1) | LU80741A1 (fr) |
NL (1) | NL7812612A (fr) |
OA (1) | OA06163A (fr) |
PL (1) | PL117790B1 (fr) |
PT (1) | PT68997A (fr) |
RO (1) | RO75807A (fr) |
SE (1) | SE434127B (fr) |
YU (1) | YU310978A (fr) |
ZA (1) | ZA787208B (fr) |
Cited By (25)
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US4356108A (en) * | 1979-12-20 | 1982-10-26 | The Mead Corporation | Encapsulation process |
US4400391A (en) * | 1980-01-09 | 1983-08-23 | The United States Of America As Represented By The Secretary Of Agriculture | Controlled release of bioactive materials using alginate gel beads |
US4409201A (en) * | 1980-05-31 | 1983-10-11 | Hoechst Aktiengesellschaft | Pressure-resistant microcapsules with a polyamide shell and a polyurethane-polyurea inner mass and process for their manufacture |
US4428983A (en) | 1980-10-16 | 1984-01-31 | Bayer Aktiengesellschaft | Process for the production of microcapsules |
US4454083A (en) * | 1981-12-21 | 1984-06-12 | Appleton Papers Inc. | Continuous microencapsulation |
US4518547A (en) * | 1983-09-15 | 1985-05-21 | Board Of Regents, The University Of Texas System | Microencapsulation process |
US4797692A (en) * | 1987-09-02 | 1989-01-10 | Xerox Corporation | Thermal ink jet printer having ink nucleation control |
US4891245A (en) * | 1986-03-21 | 1990-01-02 | Koh-I-Noor Rapidograph, Inc. | Electrophoretic display particles and a process for their preparation |
US4945121A (en) * | 1987-08-18 | 1990-07-31 | Koh-I-Noor Radiograph, Inc. | Thermosetting dyed latex colorant dispersions |
US4957681A (en) * | 1988-04-15 | 1990-09-18 | Basf Aktiengesellschaft | Preparation of pharmaceutical mixtures |
US5213934A (en) * | 1991-01-07 | 1993-05-25 | Xerox Corporation | Microcapsule toner compositions |
LT3702B (en) | 1986-07-09 | 1996-02-26 | Monsanto Co | Formulations of water-dispersible granules |
LT3915B (en) | 1986-07-09 | 1996-04-25 | Monsanto Co | Water-dispersible granules and process for the preparation thereof |
US6153657A (en) * | 1997-06-02 | 2000-11-28 | Hodogaya Chemical Co., Ltd. | Process for producing a solvent-less O/W type emulsion |
US20050075420A1 (en) * | 2003-10-06 | 2005-04-07 | Terry Stovold | Invisible ink |
US20050165131A1 (en) * | 2003-10-06 | 2005-07-28 | Terry Stovold | Invisible ink |
US20070259097A1 (en) * | 2006-03-03 | 2007-11-08 | Andersen Peder O | Method and apparatus for the preparation of capsules |
US20080113862A1 (en) * | 2003-10-06 | 2008-05-15 | Nocopi Technologies, Inc. | Invisible Ink And Scratch Pad |
US20090142406A1 (en) * | 2005-12-14 | 2009-06-04 | Sumitomo Chemicsl Comapny, Limited | Microencapsulated Pesticide |
US20090162409A1 (en) * | 2005-12-12 | 2009-06-25 | Sumitomo Chemical Company, Limited | Microencapsulated Pesticide |
US7972620B2 (en) | 2002-04-04 | 2011-07-05 | Fmc Biopolymer As | Polysaccharide capsules and methods of preparation |
WO2015023961A1 (fr) * | 2013-08-15 | 2015-02-19 | International Flavors & Fragrances Inc. | Capsules en polyurée ou polyuréthane |
US10434045B2 (en) | 2009-09-18 | 2019-10-08 | International Flavors & Fragrances Inc. | Polyurea or polyurethane capsules |
WO2020013180A1 (fr) * | 2018-07-13 | 2020-01-16 | Mitsui Chemicals, Inc. | Microcapsules de polyurée redispersibles et procédé de préparation de microcapsules de polyurée redispersibles |
US10555879B2 (en) | 2009-09-18 | 2020-02-11 | International Flavors & Fragrances Inc. | Polyurea capsule compositions |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2501059B1 (fr) * | 1981-03-09 | 1986-04-11 | Printex Sa | Procede d'obtention de microcapsules isodiametrales a diametre regle |
CA1165636A (fr) * | 1981-07-20 | 1984-04-17 | George B. Beestman | Encapsulation par polycondensation interfaciale de polymethylene polyphenylisocyanate avec une amine polyfonctionnelle en presence d'un emulsifiant a base de sulfonate de lignine |
DE3346601C2 (de) * | 1983-12-23 | 1986-06-12 | Feldmühle AG, 4000 Düsseldorf | Mikrokapseln, Verfahren zu ihrer Herstellung und ihre Verwendung in druckempfindlichen kohlefreien Durchschreibepapieren |
DE3421865A1 (de) * | 1984-06-13 | 1985-12-19 | Bayer Ag, 5090 Leverkusen | Kontinuierliche herstellung von mikrokapseldispersionen |
DE3635823A1 (de) * | 1986-10-22 | 1988-04-28 | Bayer Ag | Mikrokapseln mit verbesserten waenden |
CZ288249B6 (en) * | 1993-11-15 | 2001-05-16 | Zeneca Ltd | Microcapsule and process for producing thereof |
US5846554A (en) * | 1993-11-15 | 1998-12-08 | Zeneca Limited | Microcapsules containing suspensions of biologically active compounds and ultraviolet protectant |
US5993842A (en) * | 1994-12-12 | 1999-11-30 | Zeneca Limited | Microcapsules containing suspensions of biologically active compounds |
DE10241373A1 (de) * | 2002-09-06 | 2004-03-18 | Clariant Gmbh | Oberflächenmodifizierte Phosphinsäuresalze |
JP5028976B2 (ja) * | 2005-12-12 | 2012-09-19 | 住友化学株式会社 | 固体農薬活性化合物を含有するマイクロカプセル |
JP5028978B2 (ja) * | 2005-12-14 | 2012-09-19 | 住友化学株式会社 | 固体農薬活性化合物を含有するマイクロカプセル |
Citations (6)
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---|---|---|---|---|
US3575882A (en) * | 1963-12-13 | 1971-04-20 | Pennwalt Corp | Encapsulation process |
US3577515A (en) * | 1963-12-13 | 1971-05-04 | Pennwalt Corp | Encapsulation by interfacial polycondensation |
US3607776A (en) * | 1968-06-11 | 1971-09-21 | Pennwalt Corp | Manufacture of ingestible capsules |
DE2312059A1 (de) | 1972-03-15 | 1973-09-20 | Stauffer Chemical Co | Verfahren zum einkapseln mit wasser nicht mischbarer stoffe |
US3901687A (en) * | 1973-08-31 | 1975-08-26 | Scott & Sons Co O M | Process for the selective control of weeds in kentucky bluegrass |
US4107292A (en) * | 1974-04-01 | 1978-08-15 | Akzona Incorporated | Stable water dispersions of encapsulated parathion |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5343152B2 (fr) * | 1973-05-28 | 1978-11-17 |
-
1977
- 1977-12-30 FR FR7739950A patent/FR2413123A1/fr active Granted
-
1978
- 1978-12-20 DE DE19782855065 patent/DE2855065A1/de not_active Withdrawn
- 1978-12-21 ZA ZA00787208A patent/ZA787208B/xx unknown
- 1978-12-21 IE IE2543/78A patent/IE47702B1/en unknown
- 1978-12-22 IN IN946/DEL/78A patent/IN150286B/en unknown
- 1978-12-22 ES ES476279A patent/ES476279A1/es not_active Expired
- 1978-12-22 AU AU42883/78A patent/AU522021B2/en not_active Expired
- 1978-12-22 CA CA318,574A patent/CA1129725A/fr not_active Expired
- 1978-12-26 US US05/973,164 patent/US4309213A/en not_active Expired - Lifetime
- 1978-12-27 AT AT0929578A patent/AT365097B/de not_active IP Right Cessation
- 1978-12-27 HU HU78PI659A patent/HU180275B/hu unknown
- 1978-12-28 GB GB7850088A patent/GB2011341B/en not_active Expired
- 1978-12-28 CS CS789086A patent/CS208771B2/cs unknown
- 1978-12-28 IL IL56331A patent/IL56331A/xx unknown
- 1978-12-28 DD DD78210225A patent/DD141113A5/de unknown
- 1978-12-28 NL NL7812612A patent/NL7812612A/xx not_active Application Discontinuation
- 1978-12-28 AR AR275021A patent/AR221228A1/es active
- 1978-12-28 CH CH1322578A patent/CH643155A5/fr not_active IP Right Cessation
- 1978-12-28 RO RO7896093A patent/RO75807A/fr unknown
- 1978-12-28 YU YU03109/78A patent/YU310978A/xx unknown
- 1978-12-28 SE SE7813393A patent/SE434127B/sv not_active IP Right Cessation
- 1978-12-29 IT IT31437/78A patent/IT1102793B/it active
- 1978-12-29 PL PL1978212292A patent/PL117790B1/pl unknown
- 1978-12-29 OA OA56701A patent/OA06163A/fr unknown
- 1978-12-29 BR BR7808615A patent/BR7808615A/pt unknown
- 1978-12-29 BE BE192713A patent/BE873248A/fr not_active IP Right Cessation
- 1978-12-29 PT PT68997A patent/PT68997A/fr unknown
- 1978-12-29 JP JP16443878A patent/JPS54135671A/ja active Granted
- 1978-12-29 LU LU80741A patent/LU80741A1/fr unknown
- 1978-12-29 DK DK587378A patent/DK149341C/da not_active IP Right Cessation
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US4356108A (en) * | 1979-12-20 | 1982-10-26 | The Mead Corporation | Encapsulation process |
US4400391A (en) * | 1980-01-09 | 1983-08-23 | The United States Of America As Represented By The Secretary Of Agriculture | Controlled release of bioactive materials using alginate gel beads |
US4409201A (en) * | 1980-05-31 | 1983-10-11 | Hoechst Aktiengesellschaft | Pressure-resistant microcapsules with a polyamide shell and a polyurethane-polyurea inner mass and process for their manufacture |
US4428983A (en) | 1980-10-16 | 1984-01-31 | Bayer Aktiengesellschaft | Process for the production of microcapsules |
US4454083A (en) * | 1981-12-21 | 1984-06-12 | Appleton Papers Inc. | Continuous microencapsulation |
US4518547A (en) * | 1983-09-15 | 1985-05-21 | Board Of Regents, The University Of Texas System | Microencapsulation process |
US4891245A (en) * | 1986-03-21 | 1990-01-02 | Koh-I-Noor Rapidograph, Inc. | Electrophoretic display particles and a process for their preparation |
LT3915B (en) | 1986-07-09 | 1996-04-25 | Monsanto Co | Water-dispersible granules and process for the preparation thereof |
LT3702B (en) | 1986-07-09 | 1996-02-26 | Monsanto Co | Formulations of water-dispersible granules |
US4945121A (en) * | 1987-08-18 | 1990-07-31 | Koh-I-Noor Radiograph, Inc. | Thermosetting dyed latex colorant dispersions |
US4797692A (en) * | 1987-09-02 | 1989-01-10 | Xerox Corporation | Thermal ink jet printer having ink nucleation control |
US4957681A (en) * | 1988-04-15 | 1990-09-18 | Basf Aktiengesellschaft | Preparation of pharmaceutical mixtures |
US5213934A (en) * | 1991-01-07 | 1993-05-25 | Xerox Corporation | Microcapsule toner compositions |
US6153657A (en) * | 1997-06-02 | 2000-11-28 | Hodogaya Chemical Co., Ltd. | Process for producing a solvent-less O/W type emulsion |
US7972620B2 (en) | 2002-04-04 | 2011-07-05 | Fmc Biopolymer As | Polysaccharide capsules and methods of preparation |
US9017720B2 (en) | 2002-04-04 | 2015-04-28 | FMC Bioploymer AS | Polysaccharide capsules and method of preparation |
US20110195101A1 (en) * | 2002-04-04 | 2011-08-11 | Fmc Biopolymer As | Polysaccharide Capsules and Methods of Preparation |
US8053494B2 (en) | 2003-10-06 | 2011-11-08 | Nocopi Technologies, Inc. | Invisible ink and scratch pad |
US20080113862A1 (en) * | 2003-10-06 | 2008-05-15 | Nocopi Technologies, Inc. | Invisible Ink And Scratch Pad |
US20050075420A1 (en) * | 2003-10-06 | 2005-04-07 | Terry Stovold | Invisible ink |
US20050165131A1 (en) * | 2003-10-06 | 2005-07-28 | Terry Stovold | Invisible ink |
US8790676B2 (en) | 2005-12-12 | 2014-07-29 | Sumitomo Chemical Company, Limited | Microencapsulated pesticide |
US20090162409A1 (en) * | 2005-12-12 | 2009-06-25 | Sumitomo Chemical Company, Limited | Microencapsulated Pesticide |
US20090142406A1 (en) * | 2005-12-14 | 2009-06-04 | Sumitomo Chemicsl Comapny, Limited | Microencapsulated Pesticide |
US9060510B2 (en) | 2005-12-14 | 2015-06-23 | Sumitomo Chemical Company, Limited | Microencapsulated pesticide |
US20100266848A1 (en) * | 2006-03-03 | 2010-10-21 | Fmc Corporation | Method and Apparatus for the Preparation of Capsules |
US20070259097A1 (en) * | 2006-03-03 | 2007-11-08 | Andersen Peder O | Method and apparatus for the preparation of capsules |
US7766637B2 (en) | 2006-03-03 | 2010-08-03 | Fmc Corporation | Method and apparatus for the preparation of capsules |
US8153037B2 (en) | 2006-03-03 | 2012-04-10 | Fmc Corporation | Method and apparatus for the preparation of capsules |
US8916192B2 (en) | 2006-03-03 | 2014-12-23 | Fmc Corporation | Method and apparatus for the preparation of capsules |
US10434045B2 (en) | 2009-09-18 | 2019-10-08 | International Flavors & Fragrances Inc. | Polyurea or polyurethane capsules |
US10555879B2 (en) | 2009-09-18 | 2020-02-11 | International Flavors & Fragrances Inc. | Polyurea capsule compositions |
WO2015023961A1 (fr) * | 2013-08-15 | 2015-02-19 | International Flavors & Fragrances Inc. | Capsules en polyurée ou polyuréthane |
WO2020013180A1 (fr) * | 2018-07-13 | 2020-01-16 | Mitsui Chemicals, Inc. | Microcapsules de polyurée redispersibles et procédé de préparation de microcapsules de polyurée redispersibles |
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